JPH11117080A - Etching of metal oxide thin film - Google Patents
Etching of metal oxide thin filmInfo
- Publication number
- JPH11117080A JPH11117080A JP9281892A JP28189297A JPH11117080A JP H11117080 A JPH11117080 A JP H11117080A JP 9281892 A JP9281892 A JP 9281892A JP 28189297 A JP28189297 A JP 28189297A JP H11117080 A JPH11117080 A JP H11117080A
- Authority
- JP
- Japan
- Prior art keywords
- etching
- hydrochloric acid
- etchant
- solution
- etching solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005530 etching Methods 0.000 title claims abstract description 110
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 22
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 22
- 239000010409 thin film Substances 0.000 title claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 97
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 35
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 32
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 23
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 15
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000005259 measurement Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 80
- 230000005484 gravity Effects 0.000 claims description 35
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 9
- 229910003437 indium oxide Inorganic materials 0.000 claims description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims description 6
- AZWHFTKIBIQKCA-UHFFFAOYSA-N [Sn+2]=O.[O-2].[In+3] Chemical compound [Sn+2]=O.[O-2].[In+3] AZWHFTKIBIQKCA-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002950 deficient Effects 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- -1 and particularly Chemical compound 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は金属酸化物薄膜のエ
ッチング方法に関するものであり、さらに詳しくは、基
材表面上の酸化錫、酸化インジウム、酸化錫−酸化イン
ジウムの少なくとも一つからなる金属酸化物薄膜のエッ
チング方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for etching a metal oxide thin film, and more particularly, to a metal oxide comprising at least one of tin oxide, indium oxide, and tin oxide-indium oxide on a substrate surface. The present invention relates to a method for etching an object thin film.
【０００２】[0002]
【従来の技術】金属酸化物、とくに酸化錫、酸化インジ
ウム、酸化錫−酸化インジウムの少なくとも一つからな
る金属酸化物は、薄膜として液晶ディスプレイなどの表
示素子、太陽電池、タッチパネルなどの入力装置の透明
電極として使用されている。これらの金属酸化物のエッ
チング液としては塩酸と塩化第２鉄の混合水溶液が多用
されているが、塩酸、水の蒸発により液の組成が変化す
るため、エッチング性能が変わり、製品の仕上がりに影
響を与え不良率の増大、信頼性の低下をもたらしてい
た。2. Description of the Related Art Metal oxides, particularly metal oxides comprising at least one of tin oxide, indium oxide and tin oxide-indium oxide, are used as thin films for display devices such as liquid crystal displays, solar cells, and input devices such as touch panels. Used as a transparent electrode. A mixed aqueous solution of hydrochloric acid and ferric chloride is often used as an etchant for these metal oxides. However, since the composition of the solution changes due to the evaporation of hydrochloric acid and water, the etching performance changes, which affects the finished product. To increase the defective rate and decrease the reliability.
【０００３】近年、表示装置や入力装置は大型化すると
ともに、高密度化、微細化が行われており、より精度の
高いエッチング加工技術が求められている。[0003] In recent years, display devices and input devices have become larger, more dense and finer, and a more accurate etching technique has been demanded.
【０００４】このような問題点を解決するための試みと
して、特開平第３−１９７３３５号公報には、塩化第２
鉄および塩酸を含むエッチング液を用いるエッチング方
法において、エッチング液の酸化還元電位、比重および
／または塩酸濃度を測定し、この結果に基づきエッチン
グ液に塩酸、塩化第２鉄および水を一定の割合で供給す
る方法が開示されている。この方法は、エッチング液の
蒸発による成分変化、および基板に付着しあるいはミス
トとなって排気ダクトへ持ち出される量をあらかじめ調
べておき、それぞれの値から上記した各成分の供給比率
を算出する方法である。またこの方法によれば、精度良
くエッチング液を制御することが可能であるが、エッチ
ング加工する基板の大きさ、単位時間あたりの処理量、
ダクトの吸引力などが大きく変化すると制御が難しくな
る。例えば、単位時間あたりの処理量が多い場合を想定
し決定した各成分の供給量で液制御を行いながら処理量
を減らすと、オーバーフローで排出されるエッチング液
量が増加することになる。上記と反対の場合はエッチン
グ液量が不足しエッチング不可となる。[0004] As an attempt to solve such a problem, Japanese Patent Application Laid-Open No. Hei 3-197335 discloses a second chloride.
In an etching method using an etching solution containing iron and hydrochloric acid, the oxidation-reduction potential, specific gravity and / or hydrochloric acid concentration of the etching solution are measured, and based on the results, hydrochloric acid, ferric chloride and water are added to the etching solution at a certain ratio. A method of providing is disclosed. This method is a method in which a change in components due to evaporation of an etchant, and an amount attached to a substrate or taken out to an exhaust duct as a mist are checked in advance, and a supply ratio of each component described above is calculated from each value. is there. Further, according to this method, it is possible to control the etching solution with high accuracy, but the size of the substrate to be etched, the processing amount per unit time,
If the suction force of the duct changes greatly, control becomes difficult. For example, if the processing amount is reduced while performing the liquid control with the supply amounts of the respective components determined on the assumption that the processing amount per unit time is large, the amount of the etching liquid discharged due to the overflow increases. In the case opposite to the above, the amount of the etching solution is insufficient and etching becomes impossible.
【０００５】このような問題の解決すべく本発明者ら
は、エッチング液の比重を測定し、この測定結果に基づ
いてエッチング液に塩酸水溶液を供給し、エッチング液
の比重を設定値に調節する比重調節工程と、エッチング
液量を測定し、この測定結果に基づいてエッチング液と
同じ組成および成分含量のエッチング補給液をエッチン
グ液に供給し、エッチング液を所定量に調節する液量調
節工程とを有するエッチング方法を提案した（特願平８
−２６３２２０号）。しかしながら、前記両者のエッチ
ング方法は、何れもエッチング液の系外への持ち出し量
の大きい、換言するとエッチング液量の制御が必要な場
合に有効なものである。In order to solve such a problem, the present inventors measure the specific gravity of an etching solution, supply a hydrochloric acid aqueous solution to the etching solution based on the measurement result, and adjust the specific gravity of the etching solution to a set value. A specific gravity adjusting step, measuring the amount of the etching solution, supplying an etching replenishing solution having the same composition and component content as the etching solution to the etching solution based on the measurement result, and adjusting the etching solution to a predetermined amount; (Japanese Patent Application 8)
-263220). However, both of the above etching methods are effective when a large amount of the etchant is taken out of the system, in other words, when it is necessary to control the amount of the etchant.
【０００６】一方、エッチング装置のコストダウンやダ
ウンサイジングも従来から求められており、近年はエッ
チング液の系外への持ち出し量の少ないエッチング装置
が開発されてきている。このような装置の使用に当たっ
てはエッチング液量の制御を極力避けることが必要であ
り、エッチング液量制御を要せずにエッチング液を適正
に制御する方法が求められている。[0006] On the other hand, cost reduction and downsizing of the etching apparatus have conventionally been required, and in recent years, an etching apparatus with a small amount of an etchant taken out of the system has been developed. In using such an apparatus, it is necessary to avoid controlling the amount of the etchant as much as possible, and there is a need for a method of properly controlling the etchant without controlling the amount of the etchant.
【０００７】[0007]
【発明が解決しようとする課題】従って、本発明の目的
は、エッチング液の系外への持ち出し量の極めて少ない
エッチング装置においてもエッチング製品の不良率の増
加、信頼性の低下を防止し精度の高いエッチング加工を
可能にする金属酸化物エッチング方法を提供することに
ある。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to prevent an increase in the rejection rate of an etched product and a decrease in the reliability of an etched product even in an etching apparatus in which the amount of an etchant taken out of the system is extremely small. An object of the present invention is to provide a metal oxide etching method which enables high etching processing.
【０００８】[0008]
【課題を解決するための手段】上記課題を解決すべく鋭
意研究の結果、本発明者らは従来の課題を解決すること
を得た。即ち本発明の第１は、酸化錫、酸化インジウム
および酸化錫−酸化インジウムからなる群から選択され
た少なくとも一つの金属酸化物薄膜を基材表面上に形成
し、該薄膜を少なくとも塩酸および塩化第２鉄を含有す
る水溶液からなるエッチング液でエッチングする金属酸
化物薄膜のエッチング方法において、エッチング液の比
重を測定し、この測定結果に基づいてエッチング液に塩
酸水溶液を供給し、エッチング液の比重を設定値に調節
する比重調節工程と、エッチング液の酸化還元電位を測
定し、この測定結果に基づいてエッチング液に塩酸、塩
化第２鉄および塩化第１鉄を供給し、エッチング液の酸
化還元電位を設定値に調節する酸化還元電位調節工程
と、を有することを特徴とする金属酸化物薄膜のエッチ
ング方法である。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have solved the conventional problems. That is, a first aspect of the present invention is to form at least one metal oxide thin film selected from the group consisting of tin oxide, indium oxide, and tin oxide-indium oxide on a substrate surface, and form the thin film with at least hydrochloric acid and chloride chloride. In a method for etching a metal oxide thin film which is etched with an etching solution comprising an aqueous solution containing iron, a specific gravity of the etching solution is measured, and based on the measurement result, a hydrochloric acid aqueous solution is supplied to the etching solution, and a specific gravity of the etching solution is determined. A specific gravity adjusting step of adjusting to a set value, and measuring the oxidation-reduction potential of the etching solution, supplying hydrochloric acid, ferric chloride and ferrous chloride to the etching solution based on the measurement result, and adjusting the oxidation-reduction potential of the etching solution. And a step of adjusting the oxidation-reduction potential to a set value.
【０００９】また本発明の第２は、比重調節工程に用い
られる塩酸水溶液の代わりに、塩化第２鉄を含有する塩
酸水溶液を使用する前記の金属酸化物薄膜のエッチング
方法である。A second aspect of the present invention is the above-described method for etching a metal oxide thin film, wherein an aqueous hydrochloric acid solution containing ferric chloride is used instead of the aqueous hydrochloric acid solution used in the specific gravity adjusting step.
【００１０】[0010]
【発明の実施の形態】本発明に用いられる金属酸化物薄
膜をエッチングするエッチング液は、少なくとも塩酸お
よび塩化第２鉄を含有する水溶液からなるエッチング液
であり、とくに、酸化錫、酸化インジウム、酸化錫−酸
化インジウムの少なくとも一つからなる金属酸化物薄膜
をエッチングする場合には、好ましくは塩酸濃度１〜３
０重量％、塩化第２鉄濃度１〜４０重量％であるのがよ
く、さらに好ましくは、塩酸濃度５〜２０重量％、塩化
第２鉄濃度１５〜３５重量％がよい。BEST MODE FOR CARRYING OUT THE INVENTION An etching solution for etching a metal oxide thin film used in the present invention is an etching solution comprising an aqueous solution containing at least hydrochloric acid and ferric chloride, and particularly, tin oxide, indium oxide, and oxide oxide. When etching a metal oxide thin film composed of at least one of tin-indium oxide, preferably a hydrochloric acid concentration of 1 to 3 is used.
The concentration is preferably 0% by weight and the concentration of ferric chloride is 1 to 40% by weight, more preferably the concentration of hydrochloric acid is 5 to 20% by weight and the concentration of ferric chloride is 15 to 35% by weight.
【００１１】本発明の第１は、上記エッチング液で金属
酸化物薄膜をエッチングするに際し、次の２つの工程を
採用してエッチング液の組成および量を制御するもので
ある。即ち、エッチング液の比重を測定し、この測定結
果に基づいてエッチング液に塩酸水溶液を供給し、エッ
チング液の比重を設定値に調節する比重調節工程と、エ
ッチング液の酸化還元電位を測定し、この測定結果に基
づいてエッチング液に塩酸、塩化第２鉄および塩化第１
鉄を供給し、エッチング液の酸化還元電位を設定値に調
節する酸化還元電位調節工程である。A first aspect of the present invention is to control the composition and amount of an etching solution by employing the following two steps when etching a metal oxide thin film with the above-mentioned etching solution. That is, the specific gravity of the etching solution is measured, a hydrochloric acid aqueous solution is supplied to the etching solution based on the measurement result, a specific gravity adjusting step of adjusting the specific gravity of the etching solution to a set value, and the oxidation-reduction potential of the etching solution is measured. Based on this measurement result, hydrochloric acid, ferric chloride and ferrous chloride were added to the etching solution.
This is an oxidation-reduction potential adjustment step of supplying iron and adjusting the oxidation-reduction potential of the etching solution to a set value.
【００１２】エッチング処理中のエッチング液の組成変
化は、主に水および塩化水素の蒸発に起因し、その組成
変化はエッチング液の比重を測定することで検知するこ
とができる。従って、本発明の第１における比重調節工
程では、エッチング液の比重を測定し、この測定結果に
基づいて所定比重（濃度）とするように、蒸発で失われ
た水および塩化水素を補給するべく塩酸の水溶液をエッ
チング液に供給するものである。この結果エッチング液
組成は一定に保たれる。The change in the composition of the etching solution during the etching process is mainly caused by the evaporation of water and hydrogen chloride, and the change in the composition can be detected by measuring the specific gravity of the etching solution. Therefore, in the specific gravity adjusting step according to the first aspect of the present invention, the specific gravity of the etching solution is measured, and water and hydrogen chloride lost due to evaporation are replenished so as to have a predetermined specific gravity (concentration) based on the measurement result. An aqueous solution of hydrochloric acid is supplied to the etching solution. As a result, the composition of the etching solution is kept constant.
【００１３】ここで、供給する塩酸の水溶液における水
と塩化水素の割合（塩酸濃度）は、塩酸の水溶液の供給
によってエッチング液が所定比重（濃度）となるよう
に、蒸発によって失われる水と塩化水素の割合と同じに
設定しておく。この割合は、エッチング環境、即ち、エ
ッチング温度、スプレー圧（スプレー式の場合）、エッ
チャーの構造、排気の吸引力、排気量等により左右され
るので、実際に使用するエッチャーを使い、実際のエッ
チング条件で予備的にエッチング処理し、蒸発により失
われる水と塩化水素の割合を予め測定しておけば、容易
にこれを設定することができる。Here, the ratio of water and hydrogen chloride (hydrochloric acid concentration) in the aqueous hydrochloric acid solution to be supplied is determined so that the etching solution has a predetermined specific gravity (concentration) by supplying the aqueous hydrochloric acid solution and water and hydrogen chloride lost by evaporation. Set the same as the ratio of hydrogen. This ratio depends on the etching environment, that is, the etching temperature, the spray pressure (in the case of the spray type), the structure of the etcher, the suction force of the exhaust gas, the amount of the exhaust gas, and the like. This can be easily set by preliminarily etching under the conditions and measuring the ratio of water and hydrogen chloride lost by evaporation in advance.
【００１４】またエッチング液は、とくにスプレー式の
エッチングを行った場合などには、エッチング液が空気
中の酸素により酸化されて、エッチング液の酸化還元電
位が変化する。通常エッチングではエッチングレジスト
を使用してマスクパターンを形成し、エッチング部と非
エッチング部を形成することが多いが、エッチング液の
酸化還元電位が変化すると、エッチングレジストによっ
てはレジスト性能の低下を来すので、エッチング液の酸
化還元電位は調節が必要である。このため、本発明の第
１における酸化還元電位調節工程では、エッチング液の
酸化還元電位を測定し、この測定結果に基づいてエッチ
ング液に塩酸、塩化第２鉄および塩化第１鉄を供給し、
エッチング液の酸化還元電位を設定値に調節する。[0014] In particular, when the etching solution is spray-type etched, the etching solution is oxidized by oxygen in the air, and the oxidation-reduction potential of the etching solution changes. In normal etching, a mask pattern is formed using an etching resist, and an etched portion and a non-etched portion are often formed. However, when the oxidation-reduction potential of the etchant changes, the resist performance is lowered depending on the etching resist. Therefore, the oxidation-reduction potential of the etching solution needs to be adjusted. For this reason, in the first oxidation-reduction potential adjusting step of the present invention, the oxidation-reduction potential of the etching solution is measured, and hydrochloric acid, ferric chloride and ferrous chloride are supplied to the etching solution based on the measurement result,
The oxidation-reduction potential of the etching solution is adjusted to a set value.
【００１５】酸化還元電位調節工程における塩酸濃度
は、比重調節工程における塩酸濃度の設定値に、塩化第
１鉄が塩化第２鉄に変化するときに消費される塩酸量相
当分を増加させた濃度とすればよい。酸化還元電位調節
工程における塩化第２鉄濃度は、エッチング液の塩化第
２鉄濃度に、塩化第１鉄が空気酸化などによって塩化第
２鉄に変化することで系に供給される塩化第２鉄量相当
分を減じた濃度とすればよい。[0015] The hydrochloric acid concentration in the oxidation-reduction potential adjusting step is a concentration obtained by increasing the set value of the hydrochloric acid concentration in the specific gravity adjusting step by an amount corresponding to the amount of hydrochloric acid consumed when ferrous chloride changes to ferric chloride. And it is sufficient. The concentration of ferric chloride in the oxidation-reduction potential adjusting step is changed to the concentration of ferric chloride in the etching solution and the amount of ferric chloride supplied to the system by changing ferrous chloride to ferric chloride by air oxidation or the like. What is necessary is just to make the density | concentration which reduced the amount equivalent.
【００１６】塩化第１鉄の供給形態は限定されないが、
水溶液であることが操作上好ましい。水溶液である場
合、塩化第１鉄濃度が高ければ、酸化還元電位調節工程
で加える補給液の使用量が少なくなり、逆に低ければ使
用量は多くなるから、（少ないながらも）基板によるエ
ッチング液の持ち出し量等によるエッチング液量の減少
量を測定しておき、補給液中の塩化第１鉄濃度を決めれ
ば使用量を必要最小量とすることができる。通常、塩化
第１鉄水溶液の濃度は概ね０．１〜１重量％程度が好ま
しい。Although the supply form of ferrous chloride is not limited,
An aqueous solution is preferred for operation. In the case of an aqueous solution, if the concentration of ferrous chloride is high, the amount of the replenishing solution added in the oxidation-reduction potential adjusting step is small, and if it is low, the amount of the replenishing solution is large. If the amount of decrease in the amount of the etching solution due to the amount taken out of the replenisher is measured in advance and the concentration of ferrous chloride in the replenishing solution is determined, the amount of use can be made the necessary minimum amount. Usually, the concentration of the ferrous chloride aqueous solution is preferably about 0.1 to 1% by weight.
【００１７】酸化還元電位調節工程において、塩酸、塩
化第２鉄および塩化第１鉄は、これらを混合液として供
給するのが好ましいが、同様の割合となるよう個別に供
給することもできる。In the oxidation-reduction potential adjusting step, hydrochloric acid, ferric chloride and ferrous chloride are preferably supplied as a mixed solution, but they can also be supplied individually at the same ratio.
【００１８】本発明の第２は、第１発明と１つの工程の
みが異なる他は同様である。即ち、比重調節工程に用い
られる塩酸水溶液を、塩化第２鉄を含有する塩酸水溶液
に変更するものである。上述の第１発明の通り、本発明
においては、蒸発に起因するエッチング液組成の変化を
調整するには塩酸水溶液だけでもよいが、酸化還元電位
調節工程で加える塩化第２鉄量を減じておけば、比重調
節工程で塩化第２鉄を加えることもできる。The second aspect of the present invention is the same as the first aspect except that only one step is different. That is, the aqueous hydrochloric acid solution used in the specific gravity adjusting step is changed to an aqueous hydrochloric acid solution containing ferric chloride. As described in the first invention, in the present invention, a change in the composition of the etching solution caused by evaporation may be adjusted only with an aqueous hydrochloric acid solution, but the amount of ferric chloride added in the oxidation-reduction potential adjustment step may be reduced. For example, ferric chloride can be added in the specific gravity adjusting step.
【００１９】本発明においては、本発明の目的を阻害し
ない範囲で所望によりエッチング液に界面活性剤を添加
してもよい。In the present invention, a surfactant may be added to the etching solution, if desired, as long as the object of the present invention is not hindered.
【００２０】本発明のエッチング対象物の金属酸化物の
膜厚は通常、数１０Å〜数μｍである。The film thickness of the metal oxide to be etched of the present invention is usually several tens of degrees to several μm.
【００２１】エッチング温度はとくにに限定されない
が、概ね３０〜６０℃、スプレー圧力は０．３〜３ｋｇ
／ｃｍ2、エッチング時間は０．５〜５分とすればよ
い。The etching temperature is not particularly limited, but is generally 30 to 60 ° C., and the spray pressure is 0.3 to 3 kg.
/ Cm 2 and the etching time may be 0.5 to 5 minutes.
【００２２】[0022]
【実施例】以下、本発明を実施例および比較例によりさ
らに説明する。実施例 １ 図１に示した装置を使用し金属酸化物のエッチングを行
った。エッチャーは排気管にミストキャッチャー、冷却
塔を取り付け、ミスト、水、塩酸を回収するようにした
スプレー式の有効エッチング長さ１．８ｍ、エッチング
液保有量３００リットルのものを使用した。エッチング
対象基板の大きさは５００ｍｍ×９００ｍｍであり、
３．０ｍｍのガラス上にスパッタ法により１５００Åの
酸化錫−酸化インジウムの薄膜を形成した基板に液体フ
ォトレジストを使用し常法によりパターニングを行った
ものである。The present invention will be further described below with reference to examples and comparative examples. Example 1 A metal oxide was etched using the apparatus shown in FIG. As the etcher, a spray type effective etching length of 1.8 m, which has a mist catcher and a cooling tower attached to an exhaust pipe and collects mist, water and hydrochloric acid, and has an etching solution holding capacity of 300 liters was used. The size of the substrate to be etched is 500 mm × 900 mm,
A substrate obtained by forming a thin film of tin oxide-indium oxide at 1500 ° on a 3.0-mm glass by sputtering is patterned by a conventional method using a liquid photoresist.
【００２３】次に図１に示す装置の動作について説明す
る。エッチャー１内のエッチング液を、エッチング液の
送液ポンプ５により、エッチング液の送り配管８を通し
て比重・酸化還元電位検出制御部２に送り、エッチング
液の戻り配管９を通してエッチャー１に戻す。比重の測
定は常時行い、この結果が設定値以上になったら比重に
かかわるポンプ稼動停止信号線Ａを使って送液ポンプ６
を稼動し、送り配管１０を通して補給液貯槽３から塩酸
および塩化第２鉄水溶液をエッチャー１へ供給し、所望
の比重の設定値になたら送液ポンプ６を停止する。比重
・酸化還元電位検出制御部２では酸化還元電位の測定も
常時行い、この結果が設定値以上になったら酸化還元電
位にかかわるポンプ稼動停止信号線Ｂを使って送液ポン
プ７を稼動し、送り配管１１を通して補給液貯槽４から
塩酸、塩化第２鉄および塩化第１鉄水溶液をエッチャー
１へ供給し、所望の酸化還元電位の設定値になったら送
液ポンプ７を停止する。なお、エッチャーからのエッチ
ング液のオーバーフロー分は、配管１２を通じて系外に
排出される。Next, the operation of the apparatus shown in FIG. 1 will be described. The etching solution in the etcher 1 is sent to the specific gravity / oxidation-reduction potential detection control unit 2 through the etching solution sending pipe 8 by the etching solution sending pump 5, and returned to the etcher 1 through the etching solution return pipe 9. The specific gravity is measured at all times, and when the result exceeds the set value, the pump 6 using the pump operation stop signal line A related to the specific gravity is used.
Is operated to supply hydrochloric acid and an aqueous solution of ferric chloride from the replenishing liquid storage tank 3 to the etcher 1 through the feed pipe 10, and when the desired specific gravity is set, the liquid feed pump 6 is stopped. The specific gravity / oxidation-reduction potential detection control unit 2 always measures the oxidation-reduction potential, and when the result becomes equal to or higher than the set value, operates the liquid feed pump 7 using the pump operation stop signal line B relating to the oxidation-reduction potential, Hydrochloric acid, ferric chloride and ferrous chloride aqueous solutions are supplied to the etcher 1 from the replenishing liquid storage tank 4 through the feed pipe 11, and when the desired oxidation-reduction potential set value is reached, the liquid feed pump 7 is stopped. The overflow of the etchant from the etcher is discharged out of the system through the pipe 12.
【００２４】使用したエッチング液の塩酸濃度は１１．
７重量％、塩化第２鉄濃度は２４．３重量％である。比
重を測定しその結果に基づき供給する補給液Ａの塩酸濃
度は２０．１重量％、塩化第２鉄濃度は１３．０重量％
である。酸化還元電位を測定し、その結果に基づき供給
する補給液Ｂの塩酸濃度は１１．８重量％、塩化第２鉄
濃度は２３．９重量％、塩化第１鉄濃度は０．３５重量
％とした。エッチング条件は温度４０℃、スプレー圧力
０．８ｋｇ／ｃｍ2、コンベア速度０．９ｍ／分とし
た。The concentration of hydrochloric acid in the etching solution used is 11.
7% by weight, ferric chloride concentration 24.3% by weight. The specific gravity is measured, and based on the result, the replenisher A supplied has a hydrochloric acid concentration of 20.1% by weight and a ferric chloride concentration of 13.0% by weight.
It is. The oxidation-reduction potential was measured, and based on the results, the replenisher B supplied had a hydrochloric acid concentration of 11.8% by weight, a ferric chloride concentration of 23.9% by weight, and a ferrous chloride concentration of 0.35% by weight. did. The etching conditions were a temperature of 40 ° C., a spray pressure of 0.8 kg / cm 2 , and a conveyor speed of 0.9 m / min.
【００２５】補給液の補給方法は次のように行った。比
重を測定し、設定値＝１．２８２以上になったら補給液
Ａを自動供給し、酸化還元電位が６１０ｍＶ以上になっ
たら補給液Ｂを自動供給した。The replenishing method was performed as follows. The specific gravity was measured. When the set value was 1.282 or more, the replenishing solution A was automatically supplied, and when the oxidation-reduction potential became 610 mV or more, the replenishing solution B was automatically supplied.
【００２６】１０時間で１２０枚の基板を処理したとこ
ろエッチングにかかわる不良品の発生はなかった。ま
た、この間に供給した補給液Ａは３リットル、補給液Ｂ
は４２リットルであった。オーバーフローした排出液は
５リットルであった。When 120 substrates were processed in 10 hours, no defective products related to etching were generated. 3 L of replenishing liquid A supplied during this time and replenishing liquid B
Was 42 liters. The overflow effluent was 5 liters.
【００２７】上記の要領で一ヶ月エッチング処理を続
け、エッチャー内のエッチング液の分析を行ったとこ
ろ、次の表１のような結果を得た。液組成の制御が極め
て精度高く行われていることがわかる。なお、本実施例
１によれば補給液の供給量が適正に保たれ、液面低下が
なく廃液の発生が少なく、液交換の必要もないことが確
認された。The etching process was continued for one month in the manner described above, and the etching solution in the etcher was analyzed. The results shown in Table 1 below were obtained. It can be seen that the control of the liquid composition is performed with extremely high precision. In addition, according to the first embodiment, it was confirmed that the supply amount of the replenishing liquid was properly maintained, the liquid level did not decrease, the generation of waste liquid was small, and there was no need to change the liquid.
【００２８】[0028]
【表１】 表 １ ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ 日数 処理 酸化還元 比重 塩酸 塩化第２ インジウム 錫 枚数 電位（mV） (40℃） （％） 鉄（％） ppm ppm ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ０ − 610 1.282 11.7 24.3 − − ５ 1520 610 1.280 11.8 24.2 680 51 １０ 3010 609 1.280 11.9 24.2 1250 107 １５ 4510 608 1.281 11.9 24.3 1980 150 ２０ 6005 610 1.282 11.7 24.4 2810 275 ２５ 7120 610 1.283 11.7 24.5 2920 276 ３０ 8980 609 1.280 11.8 24.4 2830 260 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━[Table 1] Table 1 Days Treatment Redox Specific gravity Hydrochloric acid Indium Tin Number Potential (mV) (40 ℃) (%) Iron (%) ppm ppm ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ ━━━━━ 0 − 610 1.282 11.7 24.3 − − 5 1520 610 1.280 11.8 24.2 680 51 10 3010 609 1.280 11.9 24.2 1250 107 15 4510 608 1.281 11.9 24.3 1980 150 20 6005 610 1.282 11.7 24.4 2810 275 225 7120 610 1.283 11.7 24.5 2920 276 30 8980 609 1.280 11.8 24.4 2830 260 ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━
【００２９】実施例 ２ 実施例１と同じ装置を使用し、実施例１と同様の基板の
エッチングを行った。使用したエッチング液の塩酸濃度
は１５．５重量％、塩化第２鉄濃度は２１．２重量％で
ある。比重の測定結果に基づき供給する補給液Ａの塩酸
濃度は３２．０重量％（塩化第２鉄は含有しない）であ
り、酸化還元電位の測定に基づき供給する補給液Ｂの塩
酸濃度は１５．７重量％、塩化第２鉄濃度は２１．０重
量％、塩化第１鉄濃度は０．１９重量％とした。エッチ
ング温度４５℃、スプレー圧力０．８ｋｇ／ｃｍ2、コ
ンベア速度１．３ｍ／分とした。比重設定値＝１．２７
０、酸化還元電位設定値＝６３０ｍＶとし、実施例１と
同様に補給液Ａ、補給液Ｂを自動補給した。３０日間運
転した結果塩酸濃度は１５．５〜１５．２重量％、塩化
第２鉄濃度は２１．２〜２１．６重量％に制御され、供
給液量も適正に保たれ、エッチングにかかわる不良品の
発生もなかった。 Example 2 Using the same apparatus as in Example 1, the same substrate was etched as in Example 1. The used etching solution had a hydrochloric acid concentration of 15.5% by weight and a ferric chloride concentration of 21.2% by weight. The hydrochloric acid concentration of the replenishing solution A supplied based on the measurement result of the specific gravity was 32.0% by weight (not including ferric chloride), and the hydrochloric acid concentration of the replenishing solution B supplied based on the measurement of the oxidation-reduction potential was 15. The concentration of ferric chloride was 21.0% by weight, and the concentration of ferrous chloride was 0.19% by weight. The etching temperature was 45 ° C., the spray pressure was 0.8 kg / cm 2 , and the conveyor speed was 1.3 m / min. Specific gravity set value = 1.27
The replenishing liquid A and the replenishing liquid B were automatically replenished in the same manner as in Example 1 with 0, the set value of the oxidation-reduction potential = 630 mV. After 30 days of operation, the concentration of hydrochloric acid was controlled to 15.5 to 15.2% by weight, the concentration of ferric chloride was controlled to 21.2 to 21.6% by weight, the amount of the supply liquid was appropriately maintained, and the rate of etching was reduced. There was no non-defective product.
【００３０】比較例 １ 酸化還元電位を検知して補給液Ｂを供給するポンプを稼
動させない他は実施例１と同様の装置を使用し同様の処
理を行った。５時間後に回路断面形状を観察したところ
回路上部に侵食の痕跡が見られた。この時点の酸化還元
電位は６７２ｍＶであった。また、８時間後には液面低
下によりポンプが空転しエッチングが継続できなくなっ
た。COMPARATIVE EXAMPLE 1 The same processing was performed using the same apparatus as in Example 1 except that the pump for supplying the replenishing solution B upon detecting the oxidation-reduction potential was not operated. After 5 hours, the cross-sectional shape of the circuit was observed, and traces of erosion were found at the top of the circuit. The oxidation-reduction potential at this point was 672 mV. After 8 hours, the pump stopped running due to a drop in the liquid level, and etching could not be continued.
【００３１】[0031]
【発明の効果】本発明の効果は、エッチング液の系外へ
の持ち出し量の極めて少ないエッチング装置においても
エッチング製品の不良率の増加、信頼性の低下を防止し
精度の高いエッチング加工を可能にする金属酸化物エッ
チング方法を提供したことにある。The effect of the present invention is that even in an etching apparatus in which the amount of an etching solution taken out of the system is extremely small, it is possible to prevent an increase in a defective rate of an etching product and a decrease in reliability and to perform a highly accurate etching process. To provide a metal oxide etching method.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明を実施するための装置の一例を示す図で
ある。FIG. 1 is a diagram showing an example of an apparatus for implementing the present invention.
１ エッチャー ２ 比重・酸化還元電位検出制御部 ３，４ 補給液貯槽 ５ エッチング液の送液ポンプ ６，７ 補給液の送液ポンプ ８ エッチング液の送り配管 ９ エッチング液り戻り配管 １０，１１ 補給液の送り配管 Ａ エッチング液の比重にかかわるポンプ稼働停止信
号配線 Ｂ エッチング液の酸化還元電位にかかわるポンプ稼
働停止信号配線DESCRIPTION OF SYMBOLS 1 Etcher 2 Specific gravity / oxidation-reduction potential detection control part 3,4 Replenishment liquid storage tank 5 Etch liquid supply pump 6,7 Replenishment liquid supply pump 8 Etch liquid supply pipe 9 Etch liquid return pipe 10,11 Replenishment liquid Feed piping A Pump operation stop signal wiring related to specific gravity of etchant B Pump operation stop signal wiring related to oxidation-reduction potential of etchant
───────────────────────────────────────────────────── フロントページの続き (72)発明者 久保田 吉勝 東京都荒川区東尾久７丁目２番35号 旭電 化工業株式会社内 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yoshikatsu Kubota Asahi Denka Kogyo Co., Ltd., 7-35 Higashiogu, Arakawa-ku, Tokyo
Claims (2)
酸化インジウムからなる群から選択された少なくとも一
つの金属酸化物薄膜を基材表面上に形成し、該薄膜を少
なくとも塩酸および塩化第２鉄を含有する水溶液からな
るエッチング液でエッチングする金属酸化物薄膜のエッ
チング方法において、 エッチング液の比重を測定し、この測定結果に基づいて
エッチング液に塩酸水溶液を供給し、エッチング液の比
重を設定値に調節する比重調節工程と、 エッチング液の酸化還元電位を測定し、この測定結果に
基づいてエッチング液に塩酸、塩化第２鉄および塩化第
１鉄を供給し、エッチング液の酸化還元電位を設定値に
調節する酸化還元電位調節工程と、を有することを特徴
とする金属酸化物薄膜のエッチング方法。1. Tin oxide, indium oxide and tin oxide
A metal oxide thin film formed at least one metal oxide thin film selected from the group consisting of indium oxide on a substrate surface and etching the thin film with an etching solution comprising an aqueous solution containing at least hydrochloric acid and ferric chloride; In the etching method, the specific gravity of the etching solution is measured, a hydrochloric acid aqueous solution is supplied to the etching solution based on the measurement result, and a specific gravity adjusting step of adjusting the specific gravity of the etching solution to a set value is performed. Measuring, and supplying hydrochloric acid, ferric chloride and ferrous chloride to the etching solution based on the measurement result, and adjusting the oxidation-reduction potential of the etching solution to a set value. A method for etching a metal oxide thin film.
代わりに、塩化第２鉄を含有する塩酸水溶液を使用する
請求項１に記載の金属酸化物薄膜のエッチング方法。2. The method for etching a metal oxide thin film according to claim 1, wherein an aqueous hydrochloric acid solution containing ferric chloride is used instead of the aqueous hydrochloric acid solution used in the specific gravity adjusting step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9281892A JPH11117080A (en) | 1997-10-15 | 1997-10-15 | Etching of metal oxide thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9281892A JPH11117080A (en) | 1997-10-15 | 1997-10-15 | Etching of metal oxide thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11117080A true JPH11117080A (en) | 1999-04-27 |
Family
ID=17645425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9281892A Pending JPH11117080A (en) | 1997-10-15 | 1997-10-15 | Etching of metal oxide thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11117080A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100442026B1 (en) * | 2000-12-22 | 2004-07-30 | 동우 화인켐 주식회사 | Etchant for ito layer and method for the same therewith |
| WO2007003255A1 (en) * | 2005-07-04 | 2007-01-11 | Merck Patent Gmbh | Medium for etching oxidic transparent conductive layers |
| JP2009231427A (en) * | 2008-03-21 | 2009-10-08 | Toagosei Co Ltd | Etchant, method for etching transparent conductive film using etchant, substrate to be etched |
| JP2012074525A (en) * | 2010-09-28 | 2012-04-12 | Sharp Corp | Etching method and etching device |
| WO2013141232A1 (en) * | 2012-03-23 | 2013-09-26 | 三洋電機株式会社 | Solar cell and method for manufacturing same |
| JP2016025138A (en) * | 2014-07-17 | 2016-02-08 | 株式会社平間理化研究所 | Etchant management device, etchant management method, and constituent concentration measurement method of etchant |
| WO2023132286A1 (en) * | 2022-01-04 | 2023-07-13 | 東京エレクトロン株式会社 | Substrate processing apparatus and substrate processing method |
-
1997
- 1997-10-15 JP JP9281892A patent/JPH11117080A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100442026B1 (en) * | 2000-12-22 | 2004-07-30 | 동우 화인켐 주식회사 | Etchant for ito layer and method for the same therewith |
| WO2007003255A1 (en) * | 2005-07-04 | 2007-01-11 | Merck Patent Gmbh | Medium for etching oxidic transparent conductive layers |
| JP2008547232A (en) * | 2005-07-04 | 2008-12-25 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Medium for etching oxide transparent conductive layer |
| JP2009231427A (en) * | 2008-03-21 | 2009-10-08 | Toagosei Co Ltd | Etchant, method for etching transparent conductive film using etchant, substrate to be etched |
| JP2012074525A (en) * | 2010-09-28 | 2012-04-12 | Sharp Corp | Etching method and etching device |
| WO2013141232A1 (en) * | 2012-03-23 | 2013-09-26 | 三洋電機株式会社 | Solar cell and method for manufacturing same |
| JPWO2013141232A1 (en) * | 2012-03-23 | 2015-08-03 | パナソニックＩｐマネジメント株式会社 | Solar cell and manufacturing method thereof |
| JP2016025138A (en) * | 2014-07-17 | 2016-02-08 | 株式会社平間理化研究所 | Etchant management device, etchant management method, and constituent concentration measurement method of etchant |
| WO2023132286A1 (en) * | 2022-01-04 | 2023-07-13 | 東京エレクトロン株式会社 | Substrate processing apparatus and substrate processing method |
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